Abstract
Reaction of Sc strips, ScCl3, and graphite at 860-1000°C gives Sc7Cl10C2 in quantitative yields, with transport occurring at the higher temperatures; adventitious carbon will also produce the phase. The compound has been shown to be isostructural with Er7I10 by single-crystal X-ray diffraction (a=18.620 (4) Å, b=3.4975 (6) Å, c=11.810 (2) Å, β=99.81 (2)o; space group C2/m, Z=2, R=0.029, Rw=0.046 for 676 reflections, MoKα, 27Cl10, from which the heavy atom arrangement can be derived by displacement of all metal atoms by b/2 so as to convert chlorine functions on the metal chain from face-capping to edge-bridging. The driving force for this is thought to be the reduction of carbon-chlorine repulsive interactions. Core and valence XPS data for Sc7Cl10, Sc7Cl10Cl2, Sc2Cl2C, ScCl3, and Sc are presented to demonstrate the appearance of a carbide-like state for the interstitial, the presence of two different types of scandium in the first two comopounds, the oxidation of the chain that accompanies the carbon insertion, and a substantial Sc-C covalency. The latter arises through mixing of the interstitial's 2s and 2p valence orbitals with metal-metal bonding cluster orbitals of the same symmetry.
| Original language | English |
|---|---|
| Pages (from-to) | 43-58 |
| Number of pages | 16 |
| Journal | Journal of Solid State Chemistry |
| Volume | 57 |
| Issue number | 1 |
| DOIs | |
| Publication status | Published - Mar 15 1985 |
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ASJC Scopus subject areas
- Inorganic Chemistry
- Physical and Theoretical Chemistry
- Ceramics and Composites
- Electronic, Optical and Magnetic Materials
- Materials Chemistry
- Condensed Matter Physics
Cite this
Interstitial atoms in metal-metal bonded arrays : The synthesis and characterization of heptascandium decachlorodicarbide, Sc7Cl10C2, and comparison with the interstitial-free Sc7Cl10. / Hwu, Shiou Jyh; Corbett, John D.; Poeppelmeier, Kenneth R.
In: Journal of Solid State Chemistry, Vol. 57, No. 1, 15.03.1985, p. 43-58.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Interstitial atoms in metal-metal bonded arrays
T2 - The synthesis and characterization of heptascandium decachlorodicarbide, Sc7Cl10C2, and comparison with the interstitial-free Sc7Cl10
AU - Hwu, Shiou Jyh
AU - Corbett, John D.
AU - Poeppelmeier, Kenneth R
PY - 1985/3/15
Y1 - 1985/3/15
N2 - Reaction of Sc strips, ScCl3, and graphite at 860-1000°C gives Sc7Cl10C2 in quantitative yields, with transport occurring at the higher temperatures; adventitious carbon will also produce the phase. The compound has been shown to be isostructural with Er7I10 by single-crystal X-ray diffraction (a=18.620 (4) Å, b=3.4975 (6) Å, c=11.810 (2) Å, β=99.81 (2)o; space group C2/m, Z=2, R=0.029, Rw=0.046 for 676 reflections, MoKα, 27Cl10, from which the heavy atom arrangement can be derived by displacement of all metal atoms by b/2 so as to convert chlorine functions on the metal chain from face-capping to edge-bridging. The driving force for this is thought to be the reduction of carbon-chlorine repulsive interactions. Core and valence XPS data for Sc7Cl10, Sc7Cl10Cl2, Sc2Cl2C, ScCl3, and Sc are presented to demonstrate the appearance of a carbide-like state for the interstitial, the presence of two different types of scandium in the first two comopounds, the oxidation of the chain that accompanies the carbon insertion, and a substantial Sc-C covalency. The latter arises through mixing of the interstitial's 2s and 2p valence orbitals with metal-metal bonding cluster orbitals of the same symmetry.
AB - Reaction of Sc strips, ScCl3, and graphite at 860-1000°C gives Sc7Cl10C2 in quantitative yields, with transport occurring at the higher temperatures; adventitious carbon will also produce the phase. The compound has been shown to be isostructural with Er7I10 by single-crystal X-ray diffraction (a=18.620 (4) Å, b=3.4975 (6) Å, c=11.810 (2) Å, β=99.81 (2)o; space group C2/m, Z=2, R=0.029, Rw=0.046 for 676 reflections, MoKα, 27Cl10, from which the heavy atom arrangement can be derived by displacement of all metal atoms by b/2 so as to convert chlorine functions on the metal chain from face-capping to edge-bridging. The driving force for this is thought to be the reduction of carbon-chlorine repulsive interactions. Core and valence XPS data for Sc7Cl10, Sc7Cl10Cl2, Sc2Cl2C, ScCl3, and Sc are presented to demonstrate the appearance of a carbide-like state for the interstitial, the presence of two different types of scandium in the first two comopounds, the oxidation of the chain that accompanies the carbon insertion, and a substantial Sc-C covalency. The latter arises through mixing of the interstitial's 2s and 2p valence orbitals with metal-metal bonding cluster orbitals of the same symmetry.
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U2 - 10.1016/S0022-4596(85)80059-1
DO - 10.1016/S0022-4596(85)80059-1
M3 - Article
VL - 57
SP - 43
EP - 58
JO - Journal of Solid State Chemistry
JF - Journal of Solid State Chemistry
SN - 0022-4596
IS - 1
ER -